Conductive polymer composite and substrate

ABSTRACT

The present invention provides a conductive polymer composite including: (A) a π-conjugated polymer, and (B) a dopant polymer which contains a repeating unit “a” shown by the following general formula (1) and having a weight-average molecular weight in the range of 1,000 to 500,000. There can be provided a conductive polymer composite which has excellent filterability and film-formability by spin coating, and can form a conductive film having high transparency and excellent flatness. 
                         
wherein R 1  represents a hydrogen atom or a methyl group; R 2  represents any of a single bond, an ester group, and a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group optionally containing an ether group, an ester group, or both; “Z” represents any of a single bond, a phenylene group, a naphthylene group, an ether group, and an ester group; and “a” is a number satisfying 0&lt;a≦1.0.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a conductive polymer composite and asubstrate having a conductive film formed thereon from the conductivepolymer composite.

Description of the Related Art

A polymer having a conjugated double bond (i.e. π-conjugated polymer)does not show a conductivity by itself; however, if an appropriateanionic molecule is doped therein, it can express a conductivity,thereby giving a conductive polymer material (i.e. conductive polymercomposition). As to the π-conjugated polymer, polyacetylene, (hetero)aromatic polymers such as polythiophene, polyselenophene,polytellurophene, polypyrrole, and polyaniline; a mixture thereof, etc.,are used; and as to the anionic molecule (dopant), an anion of sulfonicacid type is most commonly used. This is because a sulfonic acid, whichis a strong acid, can efficiently interact with the aforementionedπ-conjugated polymers.

As to the anionic dopant of sulfonic acid type, sulfonic acid polymerssuch as polyvinyl sulfonic acid and polystyrene sulfonic acid (PSS) arewidely used (Patent Document 1). The sulfonic acid polymer includes avinylperfluoroalkyl ether sulfonic acid typified by Nafion (registeredtrademark), which is used for a fuel cell.

Polystyrene sulfonic acid (PSS), which is a sulfonic-acid homopolymer,has a sulfonic acid as a repeated monomer unit in the polymer mainchain, so that it has a high doping effect to the π-conjugated polymer,and also can enhance water dispersibility of the π-conjugated polymerafter being doped. This is because the hydrophilicity is kept due to thesulfo groups excessively present in PSS, and the dispersibility intowater is therefore enhanced dramatically.

Polythiophene having PSS as a dopant exhibits high conductivity and canbe handled as an aqueous dispersion, so that it is expected to be usedas a coating-type conductive film material in place of ITO (indium-tinoxide). As mentioned above, however, PSS is a water-soluble resin, andis hardly soluble in an organic solvent. Accordingly, the polythiophenehaving PSS as a dopant has a high hydrophilicity, but a low affinity toan organic solvent and an organic substrate, and thus, it is difficultto disperse it into an organic solvent and to form a film onto anorganic substrate.

Besides, when the polythiophene having PSS as a dopant is used in, forexample, a conductive film for an organic EL lighting, a large quantityof water tends to remain in the conductive film and the conductive filmthus formed tends to absorb moisture from an outside atmosphere sincethe polythiophene having PSS as a dopant has an extremely highhydrophilicity as mentioned above. As a result, the problems arise thatthe luminous body of the organic EL chemically changes, thereby thelight emitting capability is deteriorated, and that water agglomeratesover time and defects are caused, which results in shortening of thelifetime of the whole organic EL device. Furthermore, there arise otherproblems in the polythiophene having PSS as a dopant that particles inthe aqueous dispersion becomes large, the film surface becomes roughafter the film formation, and a non-light emitting region, called darkspot, is caused when used for the organic EL lighting.

In addition, since the polythiophene having PSS as a dopant has anabsorption at a wavelength of about 500 nm in the blue region, in thecase that this material is used as a film coating a transparentsubstrate such as a transparent electrode, there arises another problemthat when the conductivity required for the device to function is madeup by the solid concentration or the thickness of the film,transmittance of the film is affected.

Patent Document 2 discloses a conductive polymer composition composed ofa conductive polymer which contains a π-conjugated polymer formed of arepeating unit selected from thiophene, selenophene, tellurophene,pyrrole, aniline, and a polycyclic aromatic compound, and a fluorinatedacid polymer which can be wetted by an organic solvent and 50% or moreof which is neutralized by a cation; and it is shown that an aqueousdispersion of the conductive polymer can be obtained by combining water,a precursor monomer of the π-conjugated polymer, the fluorinated acidpolymer, and an oxidant, in any order.

However, in such a conventional conductive polymer, particles areagglomerated in the dispersion immediately after synthesis. Also, if anorganic solvent served as a conductive enhancer is added thereto to givea coating material, the agglomeration is further facilitated, so thatthe filterability thereof is deteriorated. If the coating material isapplied by spin coating without filtration, a flat film cannot beobtained due to the effect of the particle agglomeration; and as aresult, the problem of coating defect is caused.

Moreover, the polythiophene having PSS as a dopant can also be used as ahole injection layer. In this case, the hole injection layer is providedbetween a transparent electrode such as ITO and a light-emitting layer.The hole injection layer does not require high conductivity since theunder transparent electrode ensures the conductivity. For the holeinjection layer, no occurrence of dark spot and high hole-transportingability are required.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-146913

Patent Document 2: Japanese Patent No. 5264723

SUMMARY OF THE INVENTION

As mentioned above, the polythiophene-based conductive polymer havingPSS as a dopant, such as widely applicable PEDOT-PSS, has problems thatit has poor transparency due to absorption in the visible light althoughhaving a high conductivity; it is difficulty purified by filtrationsince it has a strong agglomeration tendency in the state of the aqueousdispersion; and the film-formability by spin coating was poor and thesurface where the film is formed was rough.

The present invention was made in view of the above-mentionedcircumstances, and an object thereof is to provide a conductive polymercomposite which has excellent filterability and film-formability by spincoating, and also can form a conductive film having high transparencyand flatness when the film is formed from the composite.

To accomplish the object, the present invention provides a conductivepolymer composite comprising:

(A) a π-conjugated polymer, and

(B) a dopant polymer which contains a repeating unit “a” shown by thefollowing general formula (1) and having a weight-average molecularweight in the range of 1,000 to 500,000,

wherein R¹ represents a hydrogen atom or a methyl group; R² representsany of a single bond, an ester group, and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon groupoptionally containing either or both of an ether group and an estergroup; “Z” represents any of a single bond, a phenylene group, anaphthylene group, an ether group, and an ester group; and “a” is anumber satisfying 0<a≦1.0.

The conductive polymer composite as mentioned above has excellentfilterability and film-formability onto an inorganic or organicsubstrate by spin coating, and also can form a conductive film havinghigh transparency and flatness when the film is formed from thecomposite.

The repeating unit “a” in the component (B) preferably includes one ormore kinds selected from repeating units a1 to a4 respectively shown bythe following general formulae (1-1) to (1-4),

wherein R¹ has the same meaning as defined above; and a1, a2, a3, and a4are each a number satisfying 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and0<a1+a2+a3+a4≦1.0.

As described above, the foregoing are preferable as the component (B)and can improve the material in filterability, film-formability,affinity to an organic solvent and an organic substrate, andtransparency after film formation.

The component (B) preferably further contains a repeating unit “b”represented by the following general formula (2),

wherein “b” is a number satisfying 0<b<1.0.

By containing the repeating unit “b”, the conductivity of the materialcan be further enhanced.

The component (B) is preferably a block copolymer.

If the component (B) is a block copolymer, the conductivity of thematerial can be further enhanced.

The component (A) is preferably a polymer formed by polymerization ofone or more precursor monomers selected from the group consisting ofpyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclicaromatic compound, and a derivative thereof.

Such monomers can be readily polymerized, and have excellent stabilityin air; and thus, the component (A) can be readily synthesized.

The conductive polymer composite preferably has dispersibility in wateror in an organic solvent.

In addition, the present invention provides a substrate having aconductive film formed thereon, wherein the conductive film is formedfrom the above-mentioned conductive polymer composite.

Thus, the conductive polymer composite of the present invention can givea conductive film by applying it onto a substrate or the like to form afilm thereon.

The conductive film thus formed has excellent conductivity andtransparency, so that it may function as a transparent electrode layer.

As mentioned above, in the conductive polymer composite of the presentinvention, the dopant polymer of the component (B) which contains asuperacidic sulfo group forms the composite together with theπ-conjugated polymer of the component (A), whereby low viscosity, goodfilterability, and superior film-formability by spin coating areprovided. In addition, when a film is formed from the inventivecomposite, a conductive film excellent in transparency, flatness, andconductivity as well as durability can be formed since the stabilitythereof to heat and light is improved. Further, the above-mentionedconductive polymer composite has excellent affinity to an organicsolvent and an organic substrate, and excellent film-formability ontoboth an organic substrate and an inorganic substrate.

In addition, the conductive film formed from the above-mentionedconductive polymer composite has excellent conductivity, transparency,and the like, so that this film may function as a transparent electrodelayer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As mentioned above, it has been desired to develop a conductivefilm-forming material which has excellent filterability andfilm-formability by spin coating, and can form a conductive film havinghigh transparency and excellent flatness when the film is formed fromthe same.

The present inventors have diligently studied to accomplish theabove-mentioned objects and consequently found that when a dopantpolymer having a repeating unit that contains sulfo group, theβ-position of which has been substituted with trifluoromethyl groups, isused in place of polystyrene sulfonic acid (PSS), which has been widelyused as a dopant of a conductive polymer material, the superacidicdopant polymer strongly interacts with the π-conjugated polymer, andtherefore, the visible light absorption region of the π-conjugatedpolymer is shifted, which leads to improvement in transparency; andfurther, the π-conjugated polymer is strongly ionically bonded to thedopant polymer, which leads to improvement in stability to light andheat. Furthermore, they found that because the filterability could beimproved, not only the film-formability by spin coating could beimproved but also higher flatness of the film could be obtained at thetiming of the film formation; thereby brought the present invention tocompletion.

That is, the present invention is a conductive polymer compositecomprising:

(A) a π-conjugated polymer, and

(B) a dopant polymer which contains a repeating unit “a” shown by thefollowing general formula (1) and having a weight-average molecularweight in the range of 1,000 to 500,000,

wherein R¹ represents a hydrogen atom or a methyl group; R² representsany of a single bond, an ester group, and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon groupoptionally containing either or both of an ether group and an estergroup; “Z” represents any of a single bond, a phenylene group, anaphthylene group, an ether group, and an ester group; and “a” is anumber satisfying 0<a≦1.0.

Hereinafter, the present invention will be described in detail, but thepresent invention is not limited thereto.

Herein, “conductive” means “electrically conductive.”

[(A) π-Conjugated Polymer]

The conductive polymer composite of the present invention contains aπ-conjugated polymer as component (A). The component (A) may be apolymer obtained by polymerization of a precursor monomer (i.e. organicmonomer molecule) to form a π-conjugated chain which is a structurehaving a single bond and a double bond alternately and successively.

Illustrative examples of the precursor monomer include monocyclicaromatic compounds such as pyrroles, thiophenes, thiophene vinylenes,selenophenes, tellurophenes, phenylenes, phenylene vinylenes, andanilines; polycyclic aromatic compounds such as acenes; and acetylenes;and a homopolymer or a copolymer of these monomers can be used as thecomponent (A).

Among these monomers, in view of easiness in polymerization andstability in air, pyrrole, thiophene, selenophene, tellurophene,aniline, a polycyclic aromatic compound, and a derivative thereof arepreferable. Particularly preferable are pyrrole, thiophene, aniline, anda derivative thereof, though not limited thereto.

If the conductive polymer composite of the present inventionparticularly contains polythiophene as the component (A), it is expectedto be developed into the application to touch panel, organic EL display,organic EL lighting, etc., because of its high conductivity and hightransparency in the visible light. On the other hand, if the conductivepolymer composite of the present invention contains polyaniline as thecomponent (A), it is difficulty applied to display and so on since itsabsorption in the visible light is larger and the conductivity thereofis lower compared with the case of containing polythiophene, but it canbe considered to use it for a top coat to prevent electric charge of theresist upper layer film by electrons in the EB (electron beam)lithography since it can be readily spin-coated because of lowviscosity.

The component (A) may attain a sufficient conductivity even if themonomers which will constitute the π-conjugated polymer is notsubstituted; however, in order to further enhance the conductivity,monomers substituted with an alkyl group, a carboxy group, a sulfogroup, an alkoxy group, a hydroxy group, a cyano group, a halogen atom,or the like may also be used.

Illustrative examples of the monomers of pyrroles, thiophenes, andanilines include pyrrole, N-methyl pyrrole, 3-methyl pyrrole, 3-ethylpyrrole, 3-n-propyl pyrrole, 3-butyl pyrrole, 3-octyl pyrrole, 3-decylpyrrole, 3-dodecyl pyrrole, 3,4-dimethyl pyrrole, 3,4-dibutyl pyrrole,3-carboxy pyrrole, 3-methyl-4-carboxy pyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutyl pyrrole, 3-hydroxy pyrrole, 3-methoxypyrrole, 3-ethoxy pyrrole, 3-butoxy pyrrole, 3-hexyloxy pyrrole, and3-methyl-4-hexyloxy pyrrole; thiophene, 3-methyl thiophene, 3-ethylthiophene, 3-propyl thiophene, 3-butyl thiophene, 3-hexyl thiophene,3-heptyl thiophene, 3-octyl thiophene, 3-decyl thiophene, 3-dodecylthiophene, 3-octadecyl thiophene, 3-bromo thiophene, 3-chloro thiophene,3-iodo thiophene, 3-cyano thiophene, 3-phenyl thiophene, 3,4-dimethylthiophene, 3,4-dibutyl thiophene, 3-hydroxy thiophene, 3-methoxythiophene, 3-ethoxy thiophene, 3-butoxy thiophene, 3-hexyloxy thiophene,3-heptyloxy thiophene, 3-octyloxy thiophene, 3-decyloxy thiophene,3-dodecyloxy thiophene, 3-octadecyloxy thiophene, 3,4-dihydroxythiophene, 3,4-dimethoxy thiophene, 3,4-diethoxy thiophene,3,4-dipropoxy thiophene, 3,4-dibutoxy thiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxy thiophene, 3,4-dioctyloxy thiophene,3,4-didecyloxy thiophene, 3,4-didodecyloxy thiophene, 3,4-ethylenedioxythiophene, 3,4-ethylenedithio thiophene, 3,4-propylenedioxy thiophene,3,4-butenedioxy thiophene, 3-methyl-4-methoxy thiophene,3-methyl-4-ethoxy thiophene, 3-carboxy thiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxymethyl thiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutyl thiophene,3,4-(2,2-dimethylpropylenedioxy)thiophene,3,4-(2,2-diethylpropylenedioxy)thiophene,(2,3-dihydrothienol[3,4-b][1,4]dioxin-2-yl)methanol; aniline, 2-methylaniline, 3-methyl aniline, 2-ethyl aniline, 3-ethyl aniline, 2-propylaniline, 3-propyl aniline, 2-butyl aniline, 3-butyl aniline, 2-isobutylaniline, 3-isobutyl aniline, 2-methoxy aniline, 2-ethoxy aniline,2-aniline sulfonic acid, and 3-aniline sulfonic acid.

Among them, a (co)polymer consisting of one or two compounds selectedfrom pyrrole, thiophene, N-methyl pyrrole, 3-methyl thiophene, 3-methoxythiophene, and 3,4-ethylenedioxy thiophene is preferably used in view ofresistance value and reactivity. Moreover, a homopolymer consisting ofpyrrole or 3,4-ethylenedioxy thiophene has high conductivity; andtherefore it is more preferable.

Meanwhile, for a practical reason, the repeat number of these repeatingunits (i.e. precursor monomers) in the component (A) is preferably inthe range of 2 to 20, more preferably 6 to 15.

In addition, the molecular weight of the component (A) is preferablyabout 130 to about 5,000.

[(B) Dopant Polymer]

The conductive polymer composite of the present invention contains adopant polymer as component (B). This dopant polymer of the component(B) is a superacidic polymer which contains a sulfonic acid, theβ-position of which has been substituted with trifluoromethyl groups,i.e. having a repeating unit “a” represented by the following generalformula (1),

wherein R¹ represents a hydrogen atom or a methyl group; R² representsany of a single bond, an ester group, and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon groupoptionally containing either or both of an ether group and an estergroup; “Z” represents any of a single bond, a phenylene group, anaphthylene group, an ether group, and an ester group; and “a” is anumber satisfying 0<a≦1.0.

In the general formula (1), R¹ is a hydrogen atom or a methyl group.

R² is any of a single bond, an ester group, and a linear, branched, orcyclic hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbongroup optionally containing either or both of an ether group and anester group. As the hydrocarbon group, for example, alkylene groups,arylene groups (such as a phenylene group and a naphthylene group),alkenylene groups are mentioned.

“Z” is any of a single bond, a phenylene group, a naphthylene group, anether group, and an ester group.

“a” is a number satisfying 0<a≦1.0, preferably satisfying 0.2≦a≦1.0.

Illustrative examples of the monomer to give the repeating unit “a”include the following compounds.

wherein R¹ has the same meaning as defined above; and “X” represents ahydrogen atom, a lithium atom, a sodium atom, a potassium atom, an aminecompound, or a sulfonium compound.

It is preferred that the repeating unit “a” shown by the general formula(1) include one or more kinds selected from repeating units a1 to a4respectively shown by the following general formulae (1-1) to (1-4).That is, among the above-exemplified monomers, monomers to giverepeating units a1 to a4 are particularly preferable,

wherein R¹ has the same meaning as defined above; and a1, a2, a3, and a4are each a number satisfying 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and0<a1+a2+a3+a4≦1.0.

By using such a component (B), the material can be improved infilterability, film-formability, affinity to an organic solvent and anorganic substrate, and transmittance after film formation.

Also, the component (B) preferably further contains a repeating unit “b”represented by the following general formula (2). By containing therepeating unit “b”, the conductivity can be further enhanced.

wherein “b” is a number satisfying 0<b<1.0.

Illustrative examples of the monomer to give the repeating unit “b”include the following compounds,

wherein X₂ represents a hydrogen atom, a lithium atom, a sodium atom, apotassium atom, an amine compound, or a sulfonium compound.

If X and/or X₂ are amine compounds, (P1a-3) described in paragraph(0048) of Japanese Patent Laid-Open Publication No. 2013-228447 may bementioned as examples.

Here, as mentioned before, “a” is a number satisfying 0<a≦1.0,preferably 0.2≦a≦1.0. If it is in the range of 0<a≦1.0 (namely, if therepeating unit “a” is contained), the effect of the present inventioncan be obtained; and if “a” is in the range of 0.2≦a1≦1.0, a highereffect thereof can be obtained. Also, if the repeating unit “a” includesone or more repeating units selected from “a1” to “a4” as mentionedabove, they are preferably 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and0<a1+a2+a3+a4≦1.0, more preferably 0≦a1≦0.9, 0≦a2≦0.9, 0≦a3≦0.9,0≦a4≦0.9, and 0.15a1+a2+a3+a4≦0.9, much more preferably 0≦a1≦0.8,0≦a2≦0.8, 0≦a3≦0.8, 0≦a4≦0.8, and 0.2≦a1+a2+a3+a4≦0.8.

If the repeating unit “b” is contained, in view of enhancing theconductivity, “b” is preferably in the range of 0.2≦b<1.0, morepreferably 0.3≦b≦0.8.

In addition, the proportion of the repeating unit “a” and the repeatingunit “b” is preferably in the range of 0.2≦a≦0.8 and 0.2≦b≦0.8, morepreferably 0.3≦a≦0.6 and 0.4≦b≦0.7.

In addition, the dopant polymer of the component (B) may contain arepeating unit “c” besides the repeating unit “a” and the repeating unit“b”; and examples of the repeating unit “c” include a styrene type, avinylnaphthalene type, a vinylsilane type, acenaphthylene, indene,benzofuran, benzothiophene, (meth)acrylic type, and vinylcarbazole.

Illustrative examples of the monomer to give the repeating unit “c”include the following compound.

The dopant polymer of the component (B) may be synthesized, for example,by a method in which intended monomers to give the repeating units “a”to “c” as mentioned above are subjected to thermal polymerization in anorganic solvent by adding a radical polymerization initiator, therebyobtaining a (co)polymer of the dopant polymer.

Examples of the organic solvent to be used in the polymerization includetoluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane,cyclopentane, methyl ethyl ketone, and γ-butyrolactone.

Examples of the radical polymerization initiator include2,2′-azobisisobutyronitrile (AIBN),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl2,2′-azobis(2-methylpropionate), benzoylperoxide, and lauroylperoxide.

The reaction temperature is preferably in the range of 50 to 80° C.; andthe reaction time is preferably in the range of 2 to 100 hours, morepreferably 5 to 20 hours.

In the dopant polymer of the component (B), the monomer to give therepeating unit “a” may be one kind or two or more kinds; and acombination of a methacryl type monomer and a styrene type monomer whichenhance the polymerizability is preferable.

In the case that two or more kinds of monomer to give the repeating unit“a” are used, the respective monomers may be copolymerized randomly oras a block. When a block-copolymerized polymer (block copolymer) isformed, the sea-island structure is formed by agglomeration among therepeating unit portions composed of respective two or more repeatingunits “a”, whereby generating a special structure around the dopantpolymer; and as a result, the merit to enhance the conductivity may beexpected.

The monomers to give the repeating units “a” to “c” may be copolymerizedrandomly, or each of these may be copolymerized as a block. In thiscase, similarly to the case of the repeating unit “a” as mentionedabove, the merit to enhance the conductivity may be expected by forminga block copolymer.

In the case that the random copolymerization is carried out by a radicalpolymerization, the polymerization is generally performed by heating amixture containing monomers to be copolymerized and a radicalpolymerization initiator. When the polymerization of a first monomer isinitiated in the presence of a radical polymerization initiator and thenfollowed by addition of a second monomer, the resulting polymer has astructure that the first monomer is polymerized at one side of thepolymer molecule, and the second monomer is polymerized at the otherside. In this case, however, the repeating units of the first and secondmonomers are mixedly present at the middle portion, thus it has adifferent structure from the block copolymer. In order to form the blockcopolymer by radical polymerization, living radical polymerization ispreferably used.

In a living radical polymerization method called RAFT polymerization(Reversible Addition Fragmentation chain Transfer polymerization),radicals at the polymer terminal are always living, so that it ispossible to form a diblock copolymer composed of a block of therepeating unit of the first monomer and a block of the repeating unit ofthe second monomer by starting the polymerization with a first monomer,and then adding a second monomer at the time when the first monomer hasbeen consumed. In addition, it is also possible to form a triblockcopolymer by starting the polymerization with a first monomer, thenadding a second monomer at the time when the first monomer has beenconsumed, and then adding a third monomer thereto.

The RAFT polymerization has the characteristic that the polymer havingnarrow molecular weight distribution (dispersity) can be obtained. Inparticular, when the RAFT polymerization is carried out by addingmonomers all at once, a polymer having further narrower molecular weightdistribution can be obtained.

Meanwhile, in the dopant polymer of the component (B), the molecularweight distribution (Mw/Mn) is preferably in the range of 1.0 to 2.0,particularly preferably in the range of narrower dispersity of 1.0 to1.5. If the dispersity is narrow, lowering of transmittance of theconductive film which is formed from the conductive polymer compositeusing this polymer can be prevented.

To carry out the RAFT polymerization, a chain transfer agent isnecessary; and illustrative examples thereof include2-cyano-2-propylbenzo thioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2-propyldodecyl trithiocarbonate,4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid,2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, cyanomethyldodecylthiocarbonate, cyanomethyl methyl(phenyl)carbamothioate,bis(thiobenzoyl) disulfide, and bis(dodecylsulfanylthiocarbonyl)disulfide. Among them, 2-cyano-2-propylbenzo thioate is especiallypreferable.

If the dopant polymer of the component (B) contains the repeating unit“c”, the proportion of the repeating units “a” to “c” is preferably inthe range of 0<a≦1.0, 0<b<1.0, and 0<c<1.0, more preferably 0.1≦a≦0.9,0.1≦b≦0.9, and 0<c≦0.8, much more preferably 0.2≦a≦0.8, 0.2≦b≦0.8, and0<c≦0.5.

Also, it is preferred that a+b+c=1.

The weight-average molecular weight of the dopant polymer of thecomponent (B) is in the range of 1,000 to 500,000, preferably 2,000 to200,000. If the weight-average molecular weight is less than 1,000, theheat resistance is insufficient, and homogeneity in the compositesolution with the component (A) becomes poor. On the other hand, if theweight-average molecular weight thereof is more than 500,000, not onlythe conductivity deteriorates but also the viscosity increases therebydeteriorating the workability and decreasing the dispersibility intowater or into an organic solvent.

The weight-average molecular weight (Mw) is a measured value in terms ofpolyethylene oxide, polyethylene glycol, or polystyrene by gelpermeation chromatography (GPC) using water, dimethylformamide (DMF), ortetrahydrofuran (THF) as a solvent.

As to the monomer to constitute the dopant polymer of the component (B),a monomer having a sulfo group may be used. Alternatively, a monomerhaving a lithium salt, a sodium salt, a potassium salt, an ammoniumsalt, or a sulfonium salt of a sulfo group may be used as a monomer toperform a polymerization reaction, and after the polymerization, thesesalts may be converted into a sulfo group by an ion-exchange resin.

[Conductive Polymer Composite]

The conductive polymer composite of the present invention includes theabove-mentioned π-conjugated polymer of the component (A) and theabove-mentioned dopant polymer of the component (B), in which the dopantpolymer of the component (B) forms the composite by coordinating withthe π-conjugated polymer of the component (A).

It is preferable that the conductive polymer composite of the presentinvention have dispersibility in water or in an organic solvent; and ifthe conductive polymer composite has such a dispersibility, thefilm-formability by spin coating onto an inorganic substrate or anorganic substrate (i.e. substrate on which an inorganic film or anorganic film has been formed) as well as the flatness of the film can bemade excellent.

(Method for Producing the Conductive Polymer Composite)

The composite of the components (A) and (B) may be obtained, forexample, by adding a raw material monomer of the component (A)(preferably pyrrole, thiophene, aniline, or a derivative monomerthereof) into an aqueous solution of the component (B) or awater/organic solvent mixed solution of the component (B), and thenadding an oxidant, and an oxidation catalyst, if needed, to perform anoxidative polymerization.

Illustrative examples of the oxidant and the oxidation catalyst includeperoxodisulfate salts (i.e. persulfate salts) such as ammoniumperoxodisulfate (i.e. ammonium persulfate), sodium peroxodisulfate (i.e.sodium persulfate), and potassium peroxodisulfate (i.e. potassiumpersulfate); transition metal compounds such as ferric chloride, ferricsulfate, and cupric chloride; metal oxides such as silver oxide andcesium oxide; peroxides such as hydrogen peroxide and ozone; organicperoxides such as benzoyl peroxide; and oxygen.

As the reaction solvent to be used for the oxidative polymerization,water or a mixture of water and a solvent may be used. As the solvent tobe used here is preferably miscible with water and can dissolve ordisperse the component (A) and the component (B). Illustrative examplethereof includes polar solvents such as N-methyl-2-pyrrolidone,N,N′-dimethylformamide, N,N′-dimethylacetamide, dimethyl sulfoxide, andhexamethyl phosphortriamide; alcohols such as methanol, ethanol,propanol, and butanol; polyvalent aliphatic alcohols such as ethyleneglycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol,1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, butanediol,1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol;carbonate compounds such as ethylene carbonate and propylene carbonate;cyclic ether compounds such as dioxane and tetrahydrofuran; chain etherssuch as dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycoldialkyl ether, propylene glycol monoalkyl ether, propylene glycoldialkyl ether, polyethylene glycol dialkyl ether, and polypropyleneglycol dialkyl ether; heterocyclic compounds such as3-methyl-2-oxazolidinone; and nitrile compounds such as acetonitrile,glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile.These solvents may be used singly or as a mixture of two or more ofthem. The blending amount of these water-miscible solvents is preferably50% by mass or less with respect to entirety of the reaction solvents.

Besides the dopant polymer of the component (B), another anion capableof being doped into the n-conjugated polymer of the component (A) may beused. As to the anion like this, an organic acid is preferable in viewof controlling the characteristic of de-doping from the π-conjugatedpolymer, and also in view of dispersibility, heat resistance,environment resistance, and so force of the conductive polymercomposite. As the organic acid, there may be mentioned an organiccarboxylic acid, phenols, an organic sulfonic acid, etc.

As to the organic carboxylic acid, acids of aliphatic, aromatic, oralicyclic compound having one, or two or more carboxy groups may beused. Illustrative examples thereof include formic acid, acetic acid,oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid,malonic acid, tartaric acid, citric acid, lactic acid, succinic acid,monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,trifluoro-acetic acid, nitroacetic acid, and triphenylacetic acid.

Illustrative example of the phenols includes cresol, phenol, andxylenol.

As to the organic sulfonic acid, acids of aliphatic, aromatic, oralicyclic compound having one, or two or more sulfo groups may be used.Illustrative examples of the compound having one sulfo group includemethanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid,1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid,1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid,1-dodecanesulfonic acid, 1-tetradecanesulfonic acid,1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid,3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid,colistinmethanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid,aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid,2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid,N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid,p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid,propylbenzenesulfonic acid, butylbenzenesulfonic acid,pentylbenzenesulfonic acid, hexylbenzenesulfonic acid,heptylbenzenesulfonic acid, octylbenzenesulfonic acid,nonylbenzenesulfonic acid, decylbenzenesulfonic acid,undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid,pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid,2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid,4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid,m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid,4-amino-3-methylbenzene-1-sulfonic acid,4-amino-5-methoxy-2-methylbenzenesulfonic acid,2-amino-5-methylbenzene-1-sulfonic acid,4-amino-2-methylbenzene-1-sulfonic acid,5-amino-2-methylbenzene-1-sulfonic acid,4-acetamide-3-chlorobenzenesulfonic acid,4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid,naphthalenesulfonic acid, methylnaphthalenesulfonic acid,propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid,pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid,4-amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1-sulfonic acid,polycondensation product of naphthalenesulfonic acid and formalin, andpolycondensation product of melaminesulfonic acid and formalin.

Illustrative examples of the compound containing two or more sulfogroups include ethane disulfonic acid, butane disulfonic acid, pentanedisulfonic acid, decane disulfonic acid, m-benzene disulfonic acid,o-benzene disulfonic acid, p-benzene disulfonic acid, toluene disulfonicacid, xylene disulfonic acid, chlorobenzene disulfonic acid,fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid,aniline-2,5-disulfonic acid, diethylbenzene disulfonic acid,dibutylbenzene disulfonic acid, naphthalene disulfonic acid,methylnaphthalene disulfonic acid, ethylnaphthalene disulfonic acid,dodecylnaphthalene disulfonic acid, pentadecylnaphthalene disulfonicacid, butylnaphthalene disulfonic acid, 2-amino-1,4-benzene disulfonicacid, 1-amino-3,8-naphthalene disulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, anthracenedisulfonic acid, butylanthracene disulfonic acid,4-acetamide-4′-isothio-cyanatostilbene-2,2′-disulfonic acid,4-acetamide-4′-isothio-cyanatostilbene-2,2′-disulfonic acid,4-acetamide-4′-maleimidylstilbene-2,2′-disulfonic acid,1-acetoxypyrene-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, and3-amino-1,5,7-naphthalene trisulfonic acid.

These anions other than the component (B) may be added, beforepolymerization of the component (A), into a solution containing a rawmaterial monomer of the component (A), the component (B), and an oxidantand/or an oxidative polymerization catalyst. Alternatively, it may beadded into the conductive polymer composite (solution) which containsthe component (A) after the polymerization and the component (B).

The composite including the component (A) and the component (B) thusobtained may be used after being pulverized by a homogenizer, a ballmill, or the like, if necessary.

For pulverization, a mixer/disperser which can apply a high shear forceis preferably used. Illustrative examples of the mixer/disperser includea homogenizer, a high-pressure homogenizer, and a bead mill; among them,a high-pressure homogenizer is particularly preferable.

Illustrative examples of the high-pressure homogenizer include NanoVater(manufactured by Yoshida Kikai Co., Ltd.), Microfluidizer (manufacturedby Powrex Corp.), and Ultimizer (manufactured by Sugino Machine Ltd.).

As the dispersion treatment using the high-pressure homogenizer, theremay be mentioned a treatment in which the composite solutions before thedispersion treatment are collided from the opposite direction with eachother under high pressure, or a treatment in which the solution ispassed through an orifice or a slit under high pressure.

Before or after the pulverization, impurities may be removed by themeasures such as filtration, ultrafiltration, and dialysis; and also,purification may be done by using a cationic ion-exchange resin, ananionic ion-exchange resin, a chelate resin, or the like.

The total content of the component (A) and the component (B) in theconductive polymer composite solution is preferably in the range of 0.05to 5.0% by mass. If the total content of the component (A) and thecomponent (B) is 0.05% by mass or more, sufficient conductivity can beobtained; and if it is 5.0% by mass or less, the uniform conductivecoating film can be readily obtained.

The content of the component (B) is preferably such an amount that thesulfo group in the component (B) is in the range of 0.1 to 10 mole, morepreferably 1 to 7 mole, per 1 mole of the component (A). If the contentof the sulfo group in the component (B) is 0.1 mole or more, the dopingeffect to the component (A) is so high that sufficient conductivity canbe secured. On the other hand, if the content of the sulfo group in thecomponent (B) is 10 mole or less, the content of the component (A) alsobecomes appropriate, so that sufficient conductivity can be obtained.

Illustrative examples of the organic solvent that can be added to thepolymerization reaction aqueous solution or can dilute the monomersinclude methanol, ethyl acetate, cyclohexanone, methyl amyl ketone,butanediol monomethyl ether, propylene glycol monomethyl ether, ethyleneglycol monomethyl ether, butanediol monoethyl ether, propylene glycolmonoethyl ether, ethylene glycol monoethyl ether, propylene glycoldimethyl ether, diethylene glycol dimethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propyleneglycol mono-tert-butyl ether acetate, γ-butyrolactone, and a mixturethereof.

The amount of the organic solvent to be used is preferably in the rangeof 0 to 1,000 mL, particularly preferably 0 to 500 mL, per 1 mole of themonomer. If the amount of the organic solvent is 1,000 mL or less, it iseconomical because the reaction vessel may not become too large.

[Other Additives]

(Surfactant)

In the present invention, a surfactant may be added to enhance thewettability to a body to be processed such as a substrate. As thesurfactant, various surfactants of nonionic, cationic, and anionic typemay be mentioned. Illustrative examples thereof include nonionicsurfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylate, sorbitan ester, andpolyoxyethylene sorbitan ester; cationic surfactants such asalkyltrimethylammonium chloride and alkylbenzylammonium chloride;anionic surfactants such as alkyl or alkylallyl sulfate salt, alkyl oralkylallyl sulfonate salt, and dialkyl sulfosuccinate salt; amphotericsurfactants such as an amino acid type and a betaine type; acetylenealcohol type surfactants; and an acetylene alcohol type surfactant whosehydroxy group is modified with polyethylene oxide or polypropyleneoxide.

(Conductivity Enhancer)

In the present invention, an organic solvent other than the main solventmay be added to enhance the conductivity of the conductive polymercomposite. The additive solvent may be exemplified by a polar solvent,and illustrative examples thereof include ethylene glycol, diethyleneglycol, polyethylene glycol, propylene glycol, dimethyl sulfoxide(DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP),sulfolane, and a mixture thereof. The adding amount is preferably in therange of 1.0 to 30.0% by mass, particularly preferably 3.0 to 10.0% bymass.

(Neutralizer)

In the present invention, an aqueous solution of the conductive polymercomposite has an acidic pH. For the purpose of neutralizing it,nitrogen-containing aromatic cyclic compound described in paragraphs(0033) to (0045) of Japanese Patent Laid-Open Publication No.2006-096975 or a cation described in paragraph (0127) of Japanese PatentNo. 5264723 may be added to adjust the solution to neutral pH. Byadjusting the pH of solution to near neutral, rust occurrence can beprevented when applied to a printer.

Thus, the conductive polymer composite of the present invention asdescribed above has excellent filterability and film-formability by spincoating, and can form a conductive film having high transparency and lowsurface roughness.

[Conductive Film]

The conductive polymer composite (solution) thus obtained can form aconductive film by applying it onto a body to be processed such as asubstrate. Illustrative examples of the method of applying theconductive polymer composite (solution) include coating by a spincoater, a bar coater, soaking, comma coating, spray coating, rollcoating, screen printing, flexographic printing, gravure printing, andink jet printing. After applying, heat treatment by using a hot-aircirculating furnace, a hot plate, or the like, or irradiation with IRlight, UV light, or the like may be carried out, whereby the conductivefilm can be formed.

As explained above, the conductive polymer composite of the presentinvention can form a conductive film by applying it onto a substrate orthe like. In addition, the conductive film thus formed can be used as atransparent electrode layer and a hole injection layer because it hasexcellent conductivity and transparency.

[Substrate]

Also, the present invention provides a substrate having a conductivefilm formed thereon, wherein the conductive film is formed from theconductive polymer composite of the present invention.

Illustrative examples of the substrate include a glass substrate, aquartz substrate, a photomask blank substrate, a resin substrate, asilicon wafer, compound semiconductor wafers such as a gallium arsenicwafer and an indium phosphorous wafer, and a flexible substrate. Inaddition, it may also be used as an anti-static top coat by applying itonto a photoresist film.

As mentioned above, in the conductive polymer composite of the presentinvention, the dopant polymer of the component (B) which contains asuperacidic sulfo group forms the composite together with thes-conjugated polymer of the component (A), whereby low viscosity, goodfilterability, and superior film-formability by spin coating areprovided. In addition, when a film is formed from the inventivecomposite, a conductive film having excellent transparency, flatness,durability, and conductivity can be formed. Further, the above-mentionedconductive polymer composite has excellent affinity to an organicsolvent and an organic substrate, and it has excellent film-formabilityonto both an organic substrate and an inorganic substrate.

In addition, the conductive film formed by the above-mentionedconductive polymer composite has excellent conductivity, transparency,and the like, so that this film may function as a transparent electrodelayer.

EXAMPLES

Hereinafter, the present invention will be specifically described withreference to Synthesis Examples, Preparation Examples, ComparativePreparation Example, Examples, and Comparative Example, but the presentinvention is not restricted thereto.

In the following, monomers used in Synthesis Examples are shown.

Monomer 1: benzyltrimethylammonium3,3,3-trifluoro-2-methacryloyloxy-2-trifluoromethylpropane-1-sulfonateMonomer 2: benzyltrimethylammonium3,3,3-trifluoro-2-(3-methacryloyloxy-1-adamantanecarbonyloxy)-2-trifluoromethylpropane-1-sulfonateMonomer 3: benzyltrimethylammonium3,3,3-trifluoro-2-trifluoromethyl-2-(4-vinylbenzoyloxy)propane-1-sulfonateMonomer 4: tetrabutylammonium3,3,3-trifluoro-2-(4-methacryloyloxy-1-benzoyloxy)-2-trifluoromethylpropane-1-sulfonate

Synthesis of Dopant Polymer Synthesis Example 1

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 48.1 g of Monomer 1 and 5.13 g ofdimethyl 2,2′-azobis(isobutyrate) had been dissolved in 112.5 g ofmethanol, over 4 hours. The mixture was further stirred at 64° C. for 4hours. After cooling to room temperature, the mixture was added dropwiseto 1,000 g of ethyl acetate under vigorous stirring. The resulting solidwas collected by filtration, and dried under vacuum at 50° C. for 15hours to obtain 26.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and theammonium salt was converted into a sulfo group by using an ion-exchangeresin. When the obtained polymer was measured by ¹⁹F-NMR, ¹H-NMR, andGPC, the following analytical results were obtained.

Weight-average molecular weight (Mw)=42,000

Molecular weight distribution (Mw/Mn)=1.61

This polymer compound was named Dopant polymer 1.

Synthesis Example 2

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 24.0 g of Monomer 1, 9.5 g of lithiumstyrenesulfonate, and 5.13 g of dimethyl 2,2′-azobis(isobutyrate) hadbeen dissolved in 112.5 g of methanol, over 4 hours. The mixture wasfurther stirred at 64° C. for 4 hours. After cooling to roomtemperature, the mixture was added dropwise to 1,000 g of ethyl acetateunder vigorous stirring. The resulting solid was collected byfiltration, and dried under vacuum at 50° C. for 15 hours to obtain 41.5g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and theammonium salt and the lithium salt were converted into sulfo groups byusing an ion-exchange resin. When the obtained polymer was measured by¹⁹F-NMR, ¹H-NMR, and GPC, the following analytical results wereobtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer 1:styrenesulfonic acid=1:1

Weight-average molecular weight (Mw)=46,000

Molecular weight distribution (Mw/Mn)=1.76

This polymer compound was named Dopant polymer 2.

Synthesis Example 3

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 32.8 g of Monomer 2, 9.5 g of lithiumstyrenesulfonate, and 5.13 g of dimethyl 2,2′-azobis(isobutyrate) hadbeen dissolved in 112.5 g of methanol, over 4 hours. The mixture wasfurther stirred at 64° C. for 4 hours. After cooling to roomtemperature, the mixture was added dropwise to 1,000 g of ethyl acetateunder vigorous stirring. The resulting solid was collected byfiltration, and dried under vacuum at 50° C. for 15 hours to obtain 46.2g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and theammonium salt and the lithium salt were converted into sulfo groups byusing an ion-exchange resin. When the obtained polymer was measured by¹⁹F-NMR, ¹H-NMR, and GPC, the following analytical results wereobtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer 2:styrenesulfonic acid=1:1

Weight-average molecular weight (Mw)=46,000

Molecular weight distribution (Mw/Mn)=1.52

This polymer compound was named Dopant polymer 3.

Synthesis Example 4

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 27.0 g of Monomer 3, 9.5 g of lithiumstyrenesulfonate, and 2.82 g of dimethyl 2,2′-azobis(isobutyrate) hadbeen dissolved in 112.5 g of methanol, over 4 hours. The mixture wasfurther stirred at 64° C. for 4 hours. After cooling to roomtemperature, the mixture was added dropwise to 1,000 g of ethyl acetateunder vigorous stirring. The resulting solid was collected byfiltration, and dried under vacuum at 50° C. for 15 hours to obtain 47.3g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and theammonium salt and the lithium salt were converted into sulfo groups byusing an ion-exchange resin. When the obtained polymer was measured by¹⁹F-NMR, ¹H-NMR, and GPC, the following analytical results wereobtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer 3:styrenesulfonic acid=1:1

Weight-average molecular weight (Mw)=55,000

Molecular weight distribution (Mw/Mn)=1.81

This polymer compound was named Dopant polymer 4.

Synthesis Example 5

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 34.6 g of Monomer 4, 9.5 g of lithiumstyrenesulfonate, and 2.82 g of dimethyl 2,2′-azobis(isobutyrate) hadbeen dissolved in 112.5 g of methanol, over 4 hours. The mixture wasfurther stirred at 64° C. for 4 hours. After cooling to roomtemperature, the mixture was added dropwise to 1,000 g of ethyl acetateunder vigorous stirring. The resulting solid was collected byfiltration, and dried under vacuum at 50° C. for 15 hours to obtain 50.2g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and theammonium salt and the lithium salt were converted into sulfo groups byusing an ion-exchange resin. When the obtained polymer was measured by¹⁹F-NMR, ¹H-NMR, and GPC, the following analytical results wereobtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer 4:styrenesulfonic acid=1:1

Weight-average molecular weight (Mw)=56,000

Molecular weight distribution (Mw/Mn)=1.68

This polymer compound was named Dopant polymer 5.

Synthesis Example 6

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 52.5 g of Monomer 2, 7.0 g of4-(1,1,1,3,3,3-hexafluoro-2-propanol)styrene, and 5.13 g of dimethyl2,2′-azobis(isobutyrate) had been dissolved in 112.5 g of methanol, over4 hours. The mixture was further stirred at 64° C. for 4 hours. Aftercooling to room temperature, the mixture was added dropwise to 1,000 gof ethyl acetate under vigorous stirring. The resulting solid wascollected by filtration, and dried under vacuum at 50° C. for 15 hoursto obtain 43.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and theammonium salt was converted into a sulfo group by using an ion-exchangeresin. When the obtained polymer was measured by ¹⁹F-NMR, ¹H-NMR, andGPC, the following analytical results were obtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer 2:4-(1,1,1,3,3,3-hexafluoro-2-propanol)styrene=4:1

Weight-average molecular weight (Mw)=41,000

Molecular weight distribution (Mw/Mn)=1.64

This polymer compound was named Dopant polymer 6.

Synthesis Example 7

Under nitrogen atmosphere, to 37.5 g of methanol stirred at 64° C. wasadded dropwise a solution in which 52.5 g of Monomer 2, 13.1 g of3,5-bis(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)cyclohexylmethacrylate, and 5.13 g of dimethyl 2,2′-azobis(isobutyrate) had beendissolved in 112.5 g of methanol, over 4 hours. The mixture was furtherstirred at 64° C. for 4 hours. After cooling to room temperature, themixture was added dropwise to 1,000 g of ethyl acetate under vigorousstirring. The resulting solid was collected by filtration, and driedunder vacuum at 50° C. for 15 hours to obtain 61.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and theammonium salt was converted into a sulfo group by using an ion-exchangeresin. When the obtained polymer was measured by ¹⁹F-NMR, ¹H-NMR, andGPC, the following analytical results were obtained.

Copolymer composition ratio (Molar ratio)

-   -   Monomer        2:3,5-bis(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)cyclohexyl        methacrylate=4:1

Weight-average molecular weight (Mw)=23,000

Molecular weight distribution (Mw/Mn)=1.61

This polymer compound was named Dopant polymer 7.

Preparation of Conductive Polymer Composite Dispersion PreparationExample 1

A solution in which 12.5 g of Dopant polymer 1 had been dissolved in1,000 mL of ultrapure water was mixed with 3.82 g of3,4-ethylenedioxythiophene at 30° C.

Into the resulting mixed solution was slowly added an oxidation catalystsolution in which 8.40 g of sodium persulfate and 2.3 g of ferricsulfate had been dissolved in 100 mL of ultrapure water while stirringthe mixed solution and keeping the temperature thereof at 30° C., andthe reaction was carried out for 4 hours under stirring.

Into the reaction solution thus obtained was added 1,000 mL of ultrapurewater, and about 1,000 mL of the solution was removed byultrafiltration. This procedure was repeated 3 times.

Subsequently, 200 mL of sulfuric acid diluted to 10% by mass and 2,000mL of ion-exchanged water were added to the solution treated with theultrafiltration, and about 2,000 mL of the treated solution was removedby ultrafiltration; then, 2,000 mL of ion-exchanged water was addedthereto, and about 2,000 mL of the solution was removed again byultrafiltration. This procedure was repeated 3 times.

Further, 2,000 mL of ion-exchanged water was added to the treatedsolution thus obtained, and about 2,000 mL of the treated solution wasremoved by ultrafiltration. This procedure was repeated 5 times toobtain Conductive polymer composite dispersion 1 having a blue colorwith a concentration of 1.3% by mass.

Conditions of the ultrafiltration were as follows.

Cut-off molecular weight of the ultrafiltration membrane: 30 K

Cross-flow method

Flow rate of the supply solution: 3,000 mL/min

Partial membrane pressure: 0.12 Pa

Meanwhile, also in other Preparation Examples, the ultrafiltration wascarried out with the same conditions.

Preparation Example 2

Procedure of Preparation Example 1 was repeated, except that 14.0 g ofDopant polymer 2 was used in place of 12.5 g of Dopant polymer 1, theblending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, theblending amount of sodium persulfate was changed to 5.31 g, and theblending amount of ferric sulfate was changed to 1.50 g, to obtainConductive polymer composite dispersion 2.

Preparation Example 3

Procedure of Preparation Example 1 was repeated, except that 13.0 g ofDopant polymer 3 was used in place of 12.5 g of Dopant polymer 1, theblending amount of 3,4-ethylenedioxythiophene was changed to 2.72 g, theblending amount of sodium persulfate was changed to 6.00 g, and theblending amount of ferric sulfate was changed to 1.60 g, to obtainConductive polymer composite dispersion 3.

Preparation Example 4

Procedure of Preparation Example 1 was repeated, except that 12.4 g ofDopant polymer 4 was used in place of 12.5 g of Dopant polymer 1, 4.50 gof ammonium persulfate was used in place of 8.40 g of sodium persulfate,the blending amount of 3,4-ethylenedioxythiophene was changed to 2.04 g,the blending amount of ferric sulfate was changed to 1.23 g, to obtainConductive polymer composite dispersion 4.

Preparation Example 5

Procedure of Preparation Example 1 was repeated, except that 13.1 g ofDopant polymer 5 was used in place of 12.5 g of Dopant polymer 1, 5.31 gof ammonium persulfate was used in place of 8.40 g of sodium persulfate,the blending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g,and the blending amount of ferric sulfate was changed to 1.50 g, toobtain Conductive polymer composite dispersion 5.

Preparation Example 6

A solution in which 14.0 g of Dopant polymer 2 had been dissolved in1,000 mL of ultrapure water was mixed with 4.65 g of3,4-ethylenedithiothiophene at 30° C.

Into the resulting mixed solution was slowly added an oxidation catalystsolution in which 8.40 g of sodium persulfate and 2.3 g of ferricsulfate had been dissolved in 100 mL of ultrapure water while stirringthe mixed solution and keeping the temperature thereof at 30° C., andthe reaction was carried out for 4 hours under stirring.

Into the reaction solution thus obtained was added 1,000 mL of ultrapurewater, and about 1,000 mL of the solution was removed byultrafiltration. This procedure was repeated 3 times.

Subsequently, 200 mL of sulfuric acid diluted to 10% by mass and 2,000mL of ion-exchanged water were added to the solution treated with theultrafiltration, and about 2,000 mL of the treated solution was removedby ultrafiltration; then, 2,000 mL of ion-exchanged water was addedthereto, and about 2,000 mL of the solution was removed again byultrafiltration. This procedure was repeated 3 times.

Further, 2,000 mL of ion-exchanged water was added to the treatedsolution thus obtained, and about 2,000 mL of the treated solution wasremoved by ultrafiltration. This procedure was repeated 5 times toobtain Conductive polymer composite dispersion 6 having a blue colorwith a concentration of 1.3% by mass.

Preparation Example 7

A solution in which 14.0 g of Dopant polymer 2 had been dissolved in1,000 mL of ultrapure water was mixed with 3.87 g of3,4-dimethoxythiophene at 30° C.

Into the resulting mixed solution was slowly added an oxidation catalystsolution in which 8.40 g of sodium persulfate and 2.3 g of ferricsulfate had been dissolved in 100 mL of ultrapure water while stirringthe mixed solution and keeping the temperature thereof at 30° C., andthe reaction was carried out for 4 hours under stirring.

Into the reaction solution thus obtained was added 1,000 mL of ultrapurewater, and about 1,000 mL of the solution was removed byultrafiltration. This procedure was repeated 3 times.

Subsequently, 200 mL of sulfuric acid diluted to 10% by mass and 2,000mL of ion-exchanged water were added to the solution treated with theultrafiltration, and about 2,000 mL of the treated solution was removedby ultrafiltration; then, 2,000 mL of ion-exchanged water was addedthereto, and about 2,000 mL of the solution was removed again byultrafiltration. This procedure was repeated 3 times.

Further, 2,000 mL of ion-exchanged water was added to the treatedsolution thus obtained, and about 2,000 mL of the treated solution wasremoved by ultrafiltration. This procedure was repeated 5 times toobtain Conductive polymer composite dispersion 7 having a blue colorwith a concentration of 1.3% by mass.

Preparation Example 8

A solution in which 14.0 g of Dopant polymer 2 had been dissolved in1,000 mL of ultrapure water was mixed with 4.62 g of(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol at 30° C.

Into the resulting mixed solution was slowly added an oxidation catalystsolution in which 8.40 g of sodium persulfate and 2.3 g of ferricsulfate had been dissolved in 100 mL of ultrapure water while stirringthe mixed solution and keeping the temperature thereof at 30° C., andthe reaction was carried out for 4 hours under stirring.

Into the reaction solution thus obtained was added 1,000 mL of ultrapurewater, and about 1,000 mL of the solution was removed byultrafiltration. This procedure was repeated 3 times.

Subsequently, 200 mL of sulfuric acid diluted to 10% by mass and 2,000mL of ion-exchanged water were added to the solution treated with theultrafiltration, and about 2,000 mL of the treated solution was removedby ultrafiltration; then, 2,000 mL of ion-exchanged water was addedthereto, and about 2,000 mL of the solution was removed again byultrafiltration. This procedure was repeated 3 times.

Further, 2,000 mL of ion-exchanged water was added to the treatedsolution thus obtained, and about 2,000 mL of the treated solution wasremoved by ultrafiltration. This procedure was repeated 5 times toobtain Conductive polymer composite dispersion 8 having a blue colorwith a concentration of 1.3% by mass.

Preparation Example 9

A solution in which 14.0 g of Dopant polymer 2 had been dissolved in1,000 mL of ultrapure water was mixed with 4.16 g of3,4-propylenedioxythiothiophene at 30° C.

Into the resulting mixed solution was slowly added an oxidation catalystsolution in which 8.40 g of sodium persulfate and 2.3 g of ferricsulfate had been dissolved in 100 mL of ultrapure water while stirringthe mixed solution and keeping the temperature thereof at 30° C., andthe reaction was carried out for 4 hours under stirring.

Into the reaction solution thus obtained was added 1,000 mL of ultrapurewater, and about 1,000 mL of the solution was removed byultrafiltration. This procedure was repeated 3 times.

Subsequently, 200 mL of sulfuric acid diluted to 10% by mass and 2,000mL of ion-exchanged water were added to the solution treated with theultrafiltration, and about 2,000 mL of the treated solution was removedby ultrafiltration; then, 2,000 mL of ion-exchanged water was addedthereto, and about 2,000 mL of the solution was removed again byultrafiltration. This procedure was repeated 3 times.

Further, 2,000 mL of ion-exchanged water was added to the treatedsolution thus obtained, and about 2,000 mL of the treated solution wasremoved by ultrafiltration. This procedure was repeated 5 times toobtain Conductive polymer composite dispersion 9 having a blue colorwith a concentration of 1.3% by mass.

Preparation Example 10

Procedure of Preparation Example 1 was repeated, except that 16.0 g ofDopant polymer 6 was used in place of 12.5 g of Dopant polymer 1, theblending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, theblending amount of sodium persulfate was changed to 5.31 g, and theblending amount of ferric sulfate was changed to 1.50 g, to obtainConductive polymer composite dispersion 10.

Preparation Example 11

Procedure of Preparation Example 1 was repeated, except that 18.0 g ofDopant polymer 7 was used in place of 12.5 g of Dopant polymer 1, theblending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, theblending amount of sodium persulfate was changed to 5.31 g, and theblending amount of ferric sulfate was changed to 1.50 g, to obtainConductive polymer composite dispersion 11.

Preparation Example 12

Conductive polymer composite dispersion 2 and Conductive polymercomposite dispersion 11 were blended in a ratio of 1:1 to obtainConductive polymer composite dispersion 12.

Comparative Preparation Example 1

A solution in which 83.3 g of an aqueous solution of polystyrenesulfonic acid (concentration of 18.0% by mass, manufactured by AldrichCo., Ltd.) had been diluted with 250 mL of ion-exchanged water was mixedwith 5.0 g of 3,4-ethylenedioxythiophene at 30° C. Except for it,procedure of Preparation Example 1 was repeated to obtain Comparativeconductive polymer composite dispersion 1 (PEDOT-PSS Dispersion) havinga blue color with a concentration of 1.3% by mass. This Comparativeconductive polymer composite dispersion 1 contained polystyrene sulfonicacid alone as a dopant polymer.

Examples

Each of the Conductive polymer composite dispersions 1 to 12 (20 g) witha concentration of 1.3% by mass obtained in Preparation Examples 1 to 12was mixed with 5 g of dimethyl sulfoxide and 0.5 g of Surfynol 465,which is a surfactant and defoamer. Then, the resulting mixture wasfiltrated by using a reproduced cellulose filter having a pore diameterof 0.45 μm (manufactured by Advantec MFS, Inc.) to prepare a conductivepolymer composition, and the respective compositions were designated asExamples 1 to 12.

Comparative Example

A conductive polymer composition was prepared in the same manner as inExamples, except for using Comparative conductive polymer compositedispersion 1 obtained in Comparative Preparation Example 1, and thecomposition was designated as Comparative Example 1.

Each of the conductive polymer compositions of Examples and ComparativeExample thus prepared was evaluated by the methods as shown below.

(Filterability)

In the preparation of the conductive polymer compositions of Examplesand Comparative Example, at the time of the filtration using thereproduced cellulose filter having a pore diameter of 0.45 μm, if thecomposition could be filtrated through the filter, this is shown by“good”, and if the composition could not be filtrated through the filterdue to clogging, this is shown by “poor” in Table 1.

(Applicability)

Firstly, the conductive polymer composition was applied by spin coatingonto a Si wafer by using 1H-360S SPINCOATER (manufactured by MIKASA Co.,Ltd.) so as to have a film thickness of 100±5 nm. Then, baking wasperformed for 5 minutes in an accuracy incubator at 120° C. to removethe solvent, thereby the conductive film was obtained. The refractiveindex (n and k) at a wavelength of 636 nm was measured with respect tothe conductive film by using VASE (manufactured by J. A. Woollam Co.,Inc.), a spectroscopic ellipsometer with the type of variable incidentangle. If the uniform film could be formed, this is shown by “good”, andif a defect derived from particles or a partial striation was found inthe film although the measurement of the refractive index could becarried out, this is shown by “poor” in Table 1.

(Transmittance)

From the refractive index (k) measured by using the spectroscopicellipsometer with the type of variable incident angle (VASE), thetransmittance of the light with a wavelength of 550 nm in a filmthickness (FT) of 200 nm was calculated. These results are shown inTable 1.

(Conductivity)

Firstly, 1.0 mL of the conductive polymer composition was dropped onto aSiO₂ wafer having a diameter of 4 inches (100 mm), and 10 seconds later,the whole wafer was spin-coated by using a spinner. The spin coatingconditions were adjusted so as to give a film thickness of 100±5 nm.Then, baking was performed for 5 minutes in an accuracy incubator at120° C. to remove the solvent, thereby the conductive film was obtained.

The conductivity (S/cm) of the conductive film thus obtained wascalculated from the surface resistivity (Ω/□) measured by Hiresta-UPMCP-HT450 and Loresta-GP MCP-T610 (both are manufactured by MitsubishiChemical corp.) and measured film thickness. These results are shown inTable 1.

(Surface Roughness)

Similarly to the evaluation method of the conductivity, the conductivefilm was formed on a SiO₂ wafer having a diameter of 4 inches (100 mm).The RMS (root mean square roughness) was measured by AFM NANO-IM-8(manufactured by Image Metrology A/S). These results are shown in Table1.

(Viscosity)

The solid concentrations of the conductive polymer compositions wereadjusted to 1.3% by mass, and the solution temperature thereof was setat 25° C. The viscosity of the composition immediately after preparationwas measured by taking 35 mL of the solution into a measurement cell forexclusive use attached to a tuning fork vibration viscometer SV-10(manufactured by A&D Co., Ltd.). These results are shown in Table 1.

TABLE 1 Transmittance Surface at wavelength Viscosity roughness of 550nm in FT Conductivity Filterability Applicability (mPa · S) (RMS, nm) of200 nm (%) (S/cm) Example 1 good good 12.7 0.11 96 102 Example 2 goodgood 19.1 0.12 95 189 Example 3 good good 20.1 0.12 96 162 Example 4good good 18.1 0.14 94 202 Example 5 good good 18.6 0.16 95 180 Example6 good good 21.9 0.19 96 190 Example 7 good good 18.9 0.11 94 168Example 8 good good 26.6 0.15 92 188 Example 9 good good 19.1 0.18 95172 Example 10 good good 9.2 0.08 97 100 Example 11 good good 8.1 0.0798 89 Example 12 good good 11.1 0.10 95 130 Comparative poor poor 65.00.28 85 460 Example 1

As shown in Table 1, Examples 1 to 12, which contained polythiophene asthe π-conjugated polymer and further contained the dopant polymer havingthe repeating unit “a”, showed excellent filterability, and also couldgive a uniform coat film by spin coating. In addition, they showed highconductivity, excellent transmittance in the visible light of I=550 nm,and excellent surface roughness.

On the other hand, Comparative Example 1, which used polystyrenesulfonic acid not having the repeating unit “a” as the dopant polymer,showed poor filterability due to high viscosity thereof, and therefore,striation derived from particles and foams by spin coating was formed onthe coat film, and a uniform coat film could not be obtained. Inaddition, the transmittance in the visible light of λ=550 nm and surfaceroughness thereof were inferior to those of Examples 1 to 12, eventhough the conductivity was higher.

As described above, it was revealed that the conductive polymercomposite of the present invention exhibits low viscosity, excellentfilterability and superior film-formability by spin coating, and alsocan form a hole injection layer and a conductive film having excellenttransparency, flatness, durability and conductivity when the film isformed from the composite.

It should be noted that the present invention is not limited to theforegoing embodiment. The embodiment is just an exemplification, and anyexamples that have substantially the same feature and demonstrate thesame functions and effects as those in the technical concept describedin claims of the present invention are included in the technical scopeof the present invention.

What is claimed is:
 1. A conductive polymer composite comprising: (A) aπ-conjugated polymer, and (B) a dopant polymer which contains arepeating unit shown by the following general formula (1) and having aweight-average molecular weight in the range of 1,000 to 500,000,

wherein R¹ represents a hydrogen atom or a methyl group; R² representsany of a single bond, an ester group, and a linear, branched, or cyclichydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon groupoptionally containing either or both of an ether group and an estergroup; “Z” represents any of a single bond, a phenylene group, anaphthylene group, an ether group, and an ester group; and “a” is anumber satisfying 0<a≦1.0.
 2. The conductive polymer composite accordingto claim 1, wherein the repeating unit shown by the general formula (1)in the component (B) includes one or more kinds selected from repeatingunits respectively shown by the following general formulae (1-1) to(1-4),

wherein R¹ has the same meaning as defined above; and a1, a2, a3, and a4are each a number satisfying 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and0<a1+a2+a3+a4≦1.0.
 3. The conductive polymer composite according toclaim 2, wherein the component (B) further contains a repeating unitshown by the following general formula (2),

wherein “b” is a number satisfying 0<b<1.0.
 4. The conductive polymercomposite according to claim 3, wherein the component (B) is a blockcopolymer.
 5. The conductive polymer composite according to claim 2,wherein the component (B) is a block copolymer.
 6. The conductivepolymer composite according to claim 2, wherein the component (A) is apolymer formed by polymerization of one or more precursor monomersselected from the group consisting of pyrrole, thiophene, selenophene,tellurophene, aniline, a polycyclic aromatic compound, and a derivativethereof.
 7. The conductive polymer composite according to claim 2,wherein the conductive polymer composite has dispersibility in water orin an organic solvent.
 8. A substrate having a conductive film formedthereon, wherein the conductive film is formed from the conductivepolymer composite according to claim
 2. 9. The conductive polymercomposite according to claim 1, wherein the component (B) furthercontains a repeating unit shown by the following general formula (2),

wherein “b” is a number satisfying 0<b<1.0.
 10. The conductive polymercomposite according to claim 9, wherein the component (B) is a blockcopolymer.
 11. The conductive polymer composite according to claim 9,wherein the component (A) is a polymer formed by polymerization of oneor more precursor monomers selected from the group consisting ofpyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclicaromatic compound, and a derivative thereof.
 12. The conductive polymercomposite according to claim 9, wherein the conductive polymer compositehas dispersibility in water or in an organic solvent.
 13. A substratehaving a conductive film formed thereon, wherein the conductive film isformed from the conductive polymer composite according to claim
 9. 14.The conductive polymer composite according to claim 1, wherein thecomponent (B) is a block copolymer.
 15. The conductive polymer compositeaccording to claim 14, wherein the component (A) is a polymer formed bypolymerization of one or more precursor monomers selected from the groupconsisting of pyrrole, thiophene, selenophene, tellurophene, aniline, apolycyclic aromatic compound, and a derivative thereof.
 16. Theconductive polymer composite according to claim 14, wherein theconductive polymer composite has dispersibility in water or in anorganic solvent.
 17. The conductive polymer composite according to claim1, wherein the component (A) is a polymer formed by polymerization ofone or more precursor monomers selected from the group consisting ofpyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclicaromatic compound, and a derivative thereof.
 18. The conductive polymercomposite according to claim 1, wherein the conductive polymer compositehas dispersibility in water or in an organic solvent.
 19. A substratehaving a conductive film formed thereon, wherein the conductive film isformed from the conductive polymer composite according to claim
 1. 20.The substrate according to claim 19, wherein the conductive filmfunctions as a transparent electrode layer.